Structural, optical and magnetic properties of Nd-doped BiFeO3 thin films prepared by pulsed laser deposition

Nd-doped BiFeO₃ thin films were grown by pulsed laser deposition on quartz substrate and their structural, optical and magnetic properties have been studied. X-ray diffraction analysis revealed that Nd addition caused structural distortion even with 5% of Nd concentration, additional secondary phase appeared in all samples but its intensity was greatly reduced with Nd addition. Doping-induced variations in texture and structure modifying both magnetic and optical properties of BiFeO₃ thin films. The energy band gap decreases while the refractive index increases with addition of Nd³⁺ in BiFeO₃ for Bi³⁺. These variations in energy band gap and refractive index have been explained on the basis of density of states and increase in disorders in the system. All the samples were found to exhibit ferromagnetism at room temperature and the saturation magnetization increases with the increase in structural distortion with addition of Nd. Finally, Nd-doping modifies the physical properties of BiFeO₃ in comparison to undoped BiFeO₃ thin films.     

The exchange bias in polycrystalline BiFeO3/Ni81Fe19 bilayers on Si substrate with LaNiO3 buffer layer

Single phase polycrystalline BiFeO₃ thin films have been grown on Si substrates using LaNiO₃ as buffer layers by pulsed laser deposition. A transmission electron microscope shows an amorphous thin layer of LaNiO₃ followed by the polycrystalline LaNiO₃, which facilitates the crystallization of a BiFeO₃ layer in R3c structure and suppression of the impurity phases. NiFe layers were deposited on the BiFeO₃ layer by magnetron sputtering. Clear exchange coupling between BiFeO₃ and NiFe (with maximum exchange bias field up to 61 Oe) has been observed at room temperature, and the exchange bias field decreases with increasing the NiFe thickness. Our results clearly demonstrate the potential application of polycrystalline BiFeO₃ in magnetoelectric coupling based spintronics.     

Effect of magnetic annealing on magnetization of BiFeO3 ceramics

The effect of magnetic annealing treatment on the magnetization of multiferroic BiFeO₃ was studied systematically. A series of pelletized nano-sized BiFeO₃ powders were annealed at high temperature under different magnetic fields. Typical ferromagnetic hysteresis loops were obtained at room temperature of the ceramics which were derived from ferromagnetic BiFeO₃ precursors. On the other hand, antiferromagnetic behaviors were observed in other samples synthesized from nonmagnetic precursors. The enhanced magnetic properties were ascribed to the magnetic anisotropy which was induced by the strong magnetic fields. This work indicates that the strong magnetic annealing method is an alternative approach to tuning the magnetic properties of high performance multiferroic materials with canted antiferromagnetic ordering.     

Investigation of a superparamagnetic phase in BiFeO8 by means of Mössbauer effect

A superparamagnetic phase in BiFeO₃ was found by means of the Mössbauer effect. This phase appears at room temperature as a doublet superimposed upon the normal BiFeO₃ six-line Mössbauer spectrum. The superparamagnetic doublet is believed to belong to small α-Fe₂O₃ particles which are superparamagnetic at room temperature. The appearance of a superparamagnetic phase may explain the weak ferromagnetism observed in BiFeO₃ in several reports.     

Multiferroic studies on (BiFeO3)m(BaTiO3)n superlattice structures

BiFeO₃ has been studied extensively due to its room temperature multiferroic features and has been proven as a promising candidate for device applications. But BiFeO₃ possesses some drawbacks like high leakage current and complicated magnetic ordering, giving rise to a canted antiferromagnetic behavior. Hence, a superlattice approach of BiFeO₃ and BaTiO₃ with a good lattice matching was fabricated and the room temperature ferroelectric and ferromagnetic properties were studied. The macroscopic and local probe studies reveal a ferroelectric nature at room temperature, and most importantly a weak ferromagnetic like behavior was observed. The ferromagnetic behavior is expected to arise due to the variation introduced in the spin modulation of single BiFeO₃ layer due to the superstructure formation.     

Structure and phase composition of BiFeO3 : La films synthesized by chemical deposition from solutions

The transmission electron microscopy, energy-dispersive, and X-ray powder diffraction analyses have been used to study the changes in the structure and phase composition of lanthanum-doped BiFeO₃ and undoped BiFeO₃ thin films synthesized by chemical deposition from solutions and annealed in the temperature range 500?C700°C. It has been found that the temperature of the onset of crystallization with formation of the rhombohedral phase of BiFeO₃ is 500°C. As the annealing temperature increases, the phase composition of the film is changed: the Bi_3.43Fe_0.57O₆ and Bi₂Fe₄O₉ phases are formed. The lanthanum doping increases the crystallization temperature to 550°C; in this case, the film remains single-phase to T = 700°C.     

Surfactant-free hydrothermal synthesis of?submicron?BiFeO3?powders

Submicron BiFeO₃ powders were successfully synthesized via a simple hydrothermal process with the assistance of mineralizer (NaOH) at 150–190°C, using FeCl₃ and Bi(NO₃)₃⋅5H₂O as reactants. The effects of mineralizer concentration, reaction temperature and time on the phase evolution and crystal morphology of the resulting samples were investigated. X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry and differential scanning calorimetry (TG-DSC), and vibrating sample magnetometry (VSM) were used to characterize the as-synthesized samples. The experimental results revealed that a pure BiFeO₃ phase could be formed at a temperature ranging from 170 to 190°C for 4–20 h in the presence of 0.03–0.12 M NaOH. It was found that the mineralizer concentration, reaction temperature and time played a key role in controlling the growing speed of nuclei and formation of BiFeO₃ crystallites. The possible formation mechanisms of submicron BiFeO₃ powders with different morphologies were presented. The magnetization of BiFeO₃ powders showed a weak ferromagnetic behavior at room temperature.     

Magnetic field annealing effects on self-oriented BiFeO3 thin films prepared by chemical solution deposition

Self-oriented BiFeO₃ (BFO) thin films are prepared via chemical solution deposition method with magnetic field in-situ annealing process. The effects of magnetic annealing on the microstructure, magnetic and dielectric properties as well as magnetoelectric coupling effect of the BFO thin films are investigated. With increasing the annealing magnetic field, the crystallization quality, texture, grain boundary connectivity and densification of the films are enhanced, which is attributed to the improvement of connection and diffusion of components. The magnetization of the field-annealing films and dielectric constant as well as remanent polarization increases with increasing the strength of annealing magnetic field. In addition, it is observed that magnetocapacitance value of the magnetic-field-annealing BFO thin film is higher than the non-field-annealing one. Moreover the BFO thin films annealed at 3 kOe magnetic field show the magnetoelectric effect with 4% under 2 kOe at room temperature.     

Structural,magnetic, and electrical properties of Gd-doped BiFeO<Subscript>3</Subscript> nanoparticles with reduced particle size

Pure and Gd-doped BiFeO₃ nanoparticles have been synthesized by sol–gel method. The significant effects of size and Gd-doping on structural, electrical, and magnetic properties have been investigated. X-ray diffraction study reveals that the pure BiFeO₃ nanoparticles possess rhombohedral structure, but with 10% Gd-doping complete structural transformation from rhombohedral to orthorhombic has been observed. The particle size of pure and Gd-doped BiFeO₃ nanoparticles, calculated using Transmission electron microscopy, has been found to be in the range 25–15 nm. Pure and Gd-doped BiFeO₃ nanoparticles show ferromagnetic character, and the magnetization increases with decrease in particle size and increase in doping concentration. Scanning electron microscopy study reveals that grain size decreases with increase in Gd concentration. Well-saturated polarization versus electric field loop is observed for the doped samples. Leakage current density decreases by four orders by doping Gd in BiFeO₃. The incorporation of Gd in BiFeO₃ enhances spin as well as electric polarization at room temperature. The possible origin of enhancement in these properties has been explained on the basis of dopant and its concentration, phase purity, small particle, and grain size.     

Polar properties of hydrothermally synthesized BiFeO3 thin films

Multiferroic bismuth ferrite (BiFeO₃) has attracted considerable attention due to applications related to the bulk photovoltaic effect in which the direction of polarization determines the direction of the photocurrent. Epitaxial thin films are produced by means of techniques that usually require high temperature processes. The hydrothermal method can be seen as an alternative route to obtain highly textured thin films in quantities compatible with batch processing; nevertheless, the structural, dielectric and electric properties are generally affected by the presence of hydrogen and other reaction by-products. In this work, functional and highly textured BiFeO₃ films were successfully produced on metallic SrTiO₃:Nb (0.5 wt.%) (100) substrates via hydrothermal synthesis. X-ray diffraction (XRD) and Atomic Force Microscopy (AFM) were used to analyze the structural properties of the films. Piezoresponse Force Microscopy (PFM) and Photoconductive Atomic Force Microscopy (Pc-AFM) were used to determine their functional properties. We show the polarization switching and confirm the presence of the bulk photovoltaic effect for the first time in hydrothermally synthesized BiFeO₃.     

Structural and magnetic properties of bulk and thin films of Mg0.95Mn0.05Fe2O4

We present here a comparative study on structural and magnetic properties of bulk and thin films of Mg_0.95Mn_0.05Fe₂O₄ ferrite deposited on two different substrates using X-ray diffraction (XRD) and dc magnetization measurements. XRD pattern indicates that the bulk sample and their thin films exhibit a polycrystalline single phase cubic spinel structure. It is found that the film deposited on indium tin oxide coated glass (ITO) substrate has smaller grain size than the film deposited on platinum coated silicon (Pt–Si) substrate. Study of magnetization hysteresis loop measurements infer that the bulk sample of Mg_0.95Mn_0.05Fe₂O₄ and its thin film deposited on Pt–Si substrate shows a well-defined hysteresis loop at room temperature, which reflects its ferrimagnetic behavior. However, the film deposited on ITO does not show any hysteresis, which reflects its superparamagnetic behavior at room temperature.     

Thickness dependent magnetic and ferroelectric properties of LaNiO3 buffered BiFeO3 thin films

BiFeO₃ (BFO) thin films with thickness increasing from 40 to 480 nm were successfully grown on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si(100) substrate and the effects of thickness evolution on magnetic and ferroelectric properties are investigated. The LNO buffer layer promotes the growth and crystallization of BFO thin films. Highly (100) orientation is induced for all BFO films regardless of the film thickness together with the dense microstructure. All BFO films exhibited weak ferromagnetic response at room temperature and saturation magnetization is found to decrease with increase in film thickness. Well saturated ferroelectric hysteresis loops were obtained for thicker films; however, the leakage current dominated the ferroelectric properties in thinner films. The leakage current density decreased by three orders of magnitude for 335 nm film compared to 40 nm film, giving rise to enhanced ferroelectric properties for thicker films. The mechanisms for the evolution of ferromagnetic and ferroelectric characteristics are discussed.     

Absence of morphotropic phase boundary effects in BiFeO<Subscript>3</Subscript>–PbTiO<Subscript>3</Subscript> thin films grown via a chemical multilayer deposition method

We report an unusual behavior observed in (BiFeO₃)_1−x –(PbTiO₃) _x (BF–xPT) thin films prepared using a multilayer chemical solution deposition method. Films of different compositions were grown by depositing several bilayers of BF and PT precursors of varying BF and PT layer thicknesses followed by heat treatment in air. X-ray diffraction showed that samples of all compositions show mixing of two compounds resulting in a single-phase mixture, also confirmed by transmission electron microscopy. In contrast to bulk compositions, samples show a monoclinic (M_A-type) structure suggesting disappearance of the morphotropic phase boundary (MPB) at x=0.30 as observed in the bulk. This is accompanied by the lack of any enhancement of the remanent polarization at the MPB, as shown by the ferroelectric measurements. Magnetic measurements showed an increase in the magnetization of the samples with increasing BF content. Significant magnetization in the samples indicates melting of spin spirals in the BF–xPT films, arising from a random distribution of iron atoms. Absence of Fe²⁺ ions was corroborated by X-ray photoelectron spectroscopy measurements. The results illustrate that thin film processing methodology significantly changes the structural evolution, in contrast to predictions from the equilibrium phase diagram, besides modifying the functional characteristics of the BP-xPT system dramatically.     

氧含量对BiFeOδ多晶陶瓷介电特性的影响

采用固相反应法制备了不同含氧量的BiFeO_δ多晶陶瓷样品，利用HP4294A阻抗分析仪测量了样品的介电特性随频率和氧含量的变化，用正电子湮没寿命谱学的方法研究了样品中因氧含量的变化所引起的结构缺陷. 实验结果表明：引入氧空位和氧填隙离子缺陷都会使介电常数减小，而介电损耗则随氧含量的增加而增加，二者的变化范围均在10%—35%之间；对不同氧含量的BiFeO_δ样品，介电常数和介电损耗随测量频率的增加而减小. 氧空位的引入使得局域电子密度变小，正电子平均寿命τ_m增加. 在氧含量δ=2.99时电子密度最大(n_e=3.90×10²³/cm³)，继续增加氧含量对正电子寿命与局域电子密度的影响不大. BiFeO_δ样品的介电常数和介电损耗随氧含量的变化可以在空间电荷限制电导的框架下来理解.     

Electrical properties of ZrO2-CeO2 at intermediate temperatures

Both ZrO₂-CeO₂ powder materials and thin film ceramic membranes have been prepared by sol-gel processes. Sol and suspensoid were used as dips for preparing the thin film membranes in this work. The membranes, with a thickness in the range of 200 nm to a few mm, were coated on porous alumina ceramic substrates by a slip-coating or spin-coating process for different purposes. The ZrO₂-CeO₂ thin film membranes are highly conductive and transparent with an ionic conductivity as high as 10⁻² S/cm at 600 °C, which is two orders of magnitude higher than that of the bulk materials. This is perhaps caused by a different microstructure for the thin film membranes compared to the bulk materials. The thin films, but not the bulk samples, are stable in reduced atmosphere. By controlling the composition and atmosphere, the ZrO₂-CeO₂ materials can be ionic, electronic or mixed conductors. For the bulk samples a transition has been observed where the conductivity increases by about two orders of magnitude. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Investigation of exchange bias in 0.1MFe2O4/0.9BiFeO3 (M=Co, Cu, Ni) nanocomposite

The 0.1MFe₂O₄/0.9BiFeO₃ (M=Co, Cu, Ni) nanocomposite samples were synthesized by the sol-gel method. Phase composition analysis was carried out, which showed that these bulk samples were composed of a ferrimagnetic MFe₂O₄ (M=Co, Cu, Ni) and a ferroelectric antiferromagnet (FEAF) BiFeO₃ phases, respectively. The magnetic properties of all the samples were investigated by measuring their magnetization as a function of temperature and magnetic field. These results indicated that the magnetic hysteresis loops of 0.1CuFe₂O₄/0.9BiFeO₃ sample sintered in air atmosphere at 550 °C for 3 h exhibited a negative shift and an enhanced coercivity at low temperature ascribed to strong exchange coupling between the BiFeO₃ and CuFe₂O₄ grains. However, there were no magnetic hysteresis loops in both the 0.1CoFe₂O₄/0.9BiFeO₃ sample and the 0.1NiFe₂O₄/0.9BiFeO₃ sample. In view of these results, we tend to think the CuFe₂O₄/BiFeO₃ nanocomposite system may be a useful multifunctional material.     

Photoluminescence study of ZnO nano-islands

ZnO nano-islands, with much more uniform size, have been grown through two-step method by metal organic chemical vapor deposition (MOCVD). The room temperature band-edge UV emission intensity of nano-islands was usually undetectable or much smaller than that of thin film. Photoluminescence (PL) emission of those nano-islands shows the high intensity nearly as that of ZnO thin film, which is great different from previous reports. By meaningfully analyzing both PL and growth condition of those three samples (bulk ZnO wafer, nano-islands and film), neutral-donor-bound-exciton (D⁰X) emission observed on ZnO nano-islands sample is eventually attributed to hydrogen and aluminum, respectively. The abnormal phenomenon of nano-islands PL intensity has been explained by the point of zinc vacancies (V_Zn) complex defects. It is considered to govern the nonradiative combination and lead enhanced intensity of UV emission in ZnO nano-islands.     

Anomalies of the phonon properties in multiferroic BiFeO3 thin films near the magnetic phase transition temperature

Size, substrate, doping and magnetic field effects on the phonon properties in multiferroic BiFeO₃ thin films are studied based on a microscopic model. We obtain an anomaly near the magnetic phase transition temperature TN which can be attributed to the magnetoelectric nature of BiFeO₃ and strong anharmonic spin-phonon interaction. It is shown that due to crystal lattice distortion for dopants with ionic radius smaller than that of the host ions the phonon energy decreases (for example Tb or Ti), whereas for the opposite case (larger radius of the doping ions, for example Co or Ni) it increases. The phonon damping is always enhanced compared to the undoped thin film.     

High optical performance and practicality of active plasmonic devices based on rhombohedral BiFeO3

First principles calculations of electronic and optical properties of multiferroic oxide BiFeO₃ are used in combination with a plasmonic device model of optical switch to show that a BiFeO₃ based device can have much better performance than devices based on existing materials. This arises from the combination of octahedral tilts, ferroelectricity and G‐type antiferromagnetism in BiFeO₃ leading to a strong dependence of the optical refractive indices on the orientation with respect to the polarization. A prototype of a plasmonic resonator with an R‐BFO thin film layer is used as an example and shows excellent switch and modulation responses. The proposed approach provides potential opportunities to develop high performance nanophotonic devices for optical communication.     

Thermal conductivity of thermoelectric Al‐substituted ZnO thin films

ZnO:Al thin films with a low electrical resistivity were grown by magnetron sputtering on sapphire substrates. The cross‐plane thermal conductivity (κ = 4.5 ± 1.3 W/mK) at room temperature is almost one order of magnitude lower than for bulk materials. The thermoelectric figure of merit ZT at elevated temperatures was estimated from in‐plane power factor and the cross‐plane thermal conductivity at room temperature. It is expected that the thermal conductivity drops with increasing temperature and is lower in‐plane than cross‐plane. Consequently, the thin film ZT is at least three times higher than for bulk samples at intermediate temperatures. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)